Method for separating squalene from deodorized distillate of vegetable oil

Abstract

The invention discloses a method for separating squalene from vegetable oil deodorized distillate, which comprises the following steps: mixing the vegetable oil deodorized distillate containing squalene with a first solvent to obtain a raw material solution, and carrying out fractional extraction on the raw material solution by using a second solvent as an extraction agent and a third solvent as a washing agent, the first solvent is selected from one or more of non-polar solvents and weak polar solvents, the second solvent is selected from one or more of polar solvents, and the third solvent is selected from one or more of non-polar solvents and weak polar solvents. The fractional extraction method adopted by the invention has the advantages of high treatment capacity, high product purity and recovery rate, low energy consumption and cost, easiness in amplification and the like, and is suitable for industrial production.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to Chinese patent application No. CN 202311574408.5 filed on November 23, 2023, and the entire contents of the above Chinese patent application are incorporated into this application by reference. Technical Field

[0003] The present application relates to the field of chemical engineering technology, and in particular to a method for separating squalene from a deodorized distillate of a vegetable oil. Background Art

[0004] Squalene is a teraconite containing six isoprene unsaturated bonds and belongs to the terpene class of compounds. Squalene has antioxidant, anti-cancer, anti-inflammatory, antioxidant and anti-diabetic activities and is widely used in cosmetics, health products, medicine and other fields.

[0005] Deodorized distillate is a byproduct formed by steam distillation deodorization during the vegetable oil refining process, and its components vary depending on the plant source and deodorization process. The main components of vegetable oil deodorization distillate (DD oil) are free fatty acids (30-60%), glycerides (10-20%), vitamin E (1-20%), phytosterols (10-30%) and a small amount of squalene. It is a good raw material for natural vitamin E, phytosterols, and fatty acids / esters; but the squalene content is relatively low and the extraction is difficult. Therefore, developing an efficient separation and purification process to extract squalene from plant deodorized distillates is an effective way to achieve the preparation of squalene from plant sources.

[0006] At present, the method of separating squalene from the deodorized distillate of vegetable oil often adopts a plurality of process couplings. First, some active components or impurities are separated by pretreatment such as esterification, cold analysis / filtering, molecular distillation / multiple distillations (WO / 2010 / 004193 and CN102089263A) to obtain a raw material enriched with squalene. For example, Chinese patent CN103483305B uses high pressure crystallization combined with urea bag method to achieve rapid impurity removal and partial deacidification, and obtains a mixture with high vitamin E and squalene content after deacidification again; Chinese patent CN107474093A discloses a method of separating vitamin E, sterols, methyl esters, glycerol, squalene and high boiling products by enzymatic esterification, cold analysis, and molecular distillation coupling, but the squalene content is only 10-20%. It can be seen that it is necessary to develop a process with high separation selectivity for squalene to obtain high-purity squalene.

[0007] At present, high-purity squalene products can be obtained by multi-stage distillation (WO / 2010 / 004193, CN102089263A), multi-stage distillation (CN202211106716.0), adsorption separation (Chinese patent CN 105949025A, CN 103708992B), extraction (CN101830770B) and other methods. Chinese patent CN202211106716.0 discloses a method for obtaining plant sterols, squalene, natural vitamin E and fatty acid alkyl esters from plant deodorization distillates through esterification, cold analysis / pressure filtration and multi-stage distillation. Distillation is a high-energy unit operation, and the temperature of the distillation tower is relatively high (170-210°C), which will produce by-products and affect the yield. Chinese patent CN 105949025 A discloses a method for separating squalene from plant oil deodorization distillates by adsorption using D101 macroporous adsorption resin. Chinese patent CN 103708992B discloses a method for extracting squalene from vegetable oil deodorized distillate by secondary column chromatography, using alkaline anion exchange resin and silica gel as primary and secondary column fillers, respectively. However, the squalene content in the product is about 50%, and the purity needs to be improved. Chinese patent CN101830770B uses vegetable oil deodorized distillate as raw material, and molecularly distills the unsaponifiable matter twice, combining crystallization and extraction to obtain phytosterols, squalene and mixed tocopherols. The extraction stage of this method uses a liquid-liquid two-phase system composed of n-hexane-methanol, and the separation efficiency needs to be improved.

[0008] Extraction separation is a commonly used separation method in industry. Patent CN 106588542A discloses a method for separating squalene from the invaluable acid oil of vitamin E and phytosterols separated from plant deodorized distillates by single-stage liquid-liquid extraction. After single-stage liquid-liquid extraction and decolorization, the raffinate phase obtains squalene with a purity of 75-90%; Patent CN103804337A uses plant oil deodorized distillates as raw materials, obtains light boiling point components containing vitamin E and squalene through esterification reaction, glycerol decomposition reaction, and short-path distillation, and then separates the two through multi-stage countercurrent liquid-liquid extraction. The raffinate phase rich in squalene is crystallized at low temperature to obtain squalene with a content of 93.5% and a yield of 91.7%. Although the above methods can obtain squalene with improved purity, due to the limitations of the single-stage liquid-liquid extraction and countercurrent liquid-liquid extraction operation modes, there are still problems of insufficient purity and low yield of squalene. Therefore, there is an urgent need to develop a process route with low energy consumption, high throughput, high product yield, high product purity, and easy scalability for separating squalene from plant deodorization distillates. Summary of the invention

[0009] In order to solve the problems of high cost, high operating temperature, large consumption of organic solvent, etc. in the existing extraction and separation of squalene from vegetable oil deodorization distillate, the present application provides a method for separating squalene from vegetable oil deodorization distillate.

[0010] To achieve the above object, the present application provides a method for separating squalene from a deodorized plant oil distillate by using a fractionation extraction method, which comprises mixing the deodorized plant oil distillate containing squalene with a first solvent to obtain a raw material liquid, and fractionating and extracting the raw material liquid using a second solvent as an extractant and a third solvent as a detergent.

[0011] The first solvent is selected from one or more of non-polar solvents and weak polar solvents, the second solvent is selected from one or more of polar solvents, and the third solvent is selected from one or more of non-polar solvents and weak polar solvents.

[0012] The present application is based on the structural differences between squalene and other components in the vegetable oil deodorization distillate. In view of the fact that squalene is a 30-carbon hexaene structure, the polarity is weak, and the tocopherol, glyceride, phytosterol and fatty acid in the vegetable oil deodorization distillate contain one or more polar groups such as phenolic hydroxyl, ester group, hydroxyl, carboxylic acid group, etc., and compared with squalene, the polarity of these substances is stronger. Therefore, in the liquid-liquid two-phase system constructed by non- / weakly polar-polar solvents, squalene is easy to distribute in the non-polar phase, and the components with polar groups are more soluble in polar solvents, thereby realizing the selective separation of squalene. At the same time, fractional extraction consists of an extraction section and a washing section. The introduction of the washing section can significantly improve product purity and recovery, and is more suitable for industrial production.

[0013] In some embodiments, the present application provides a method for separating squalene from a vegetable oil deodorant distillate by fractional extraction, the method comprising dissolving the vegetable oil deodorant distillate in a non-polar solvent, performing fractional extraction using a polar solvent as an extractant and using the same detergent as the raw material solvent.

[0014] Compared with the reported steam / distillation method, the extraction method proposed in this application has higher separation selectivity and lower energy consumption; compared with the reported adsorption chromatography method, it has the advantages of simple operation, easy continuous operation, low organic solvent consumption, low cost, etc. Compared with single-stage liquid-liquid extraction and countercurrent liquid-liquid extraction, fractional extraction consists of an extraction section and a washing section. The introduction of the washing section can significantly improve the product purity and recovery rate, and is suitable for industrial production.

[0015] In some embodiments, the vegetable oil deodorized distillate containing squalene includes one or more of the whole components of the vegetable oil deodorized distillate or its esterification products, the components of the vegetable oil deodorized distillate or its esterification products from which tocopherol and / or phytosterol are removed, and the vegetable oil deodorized distillate components enriched with squalene.

[0016] In some embodiments, the vegetable oil deodorized distillate containing squalene is selected from the vegetable oil deodorized distillate or the component of its esterification product from which tocopherol and / or phytosterol are removed, or the vegetable oil deodorized distillate enriched with squalene.

[0017] In some embodiments, the raw material is a deodorized plant oil distillate containing squalene, including all components of the deodorized plant oil distillate or the esterification product of the deodorized plant oil distillate, components from which tocopherol and / or phytosterol are removed, components enriched in squalene, etc. In some preferred embodiments, in order to achieve comprehensive utilization of the deodorized plant oil distillate, the raw material is one of the components from which tocopherol and / or phytosterol are removed and the components enriched in squalene in the deodorized plant oil distillate or the esterification product of the deodorized plant oil distillate.

[0018] In some embodiments, the squalene content in the vegetable oil deodorization distillate containing squalene is 5wt%-50%, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or any value therebetween.

[0019] In some embodiments, the vegetable oil deodorized distillate is selected from one or more of soybean oil deodorized distillate, rice bran oil deodorized distillate, rapeseed oil deodorized distillate, camellia oil deodorized distillate and olive oil deodorized distillate.

[0020] In some embodiments, the non-polar solvent and / or weak polar solvent includes one or more of straight-chain alkanes with a carbon number of 5-12, branched-chain alkanes with a carbon number of 5-12, cyclic saturated alkanes with a carbon number of 5-12, straight-chain olefins with a carbon number of 5-12, branched-chain olefins with a carbon number of 5-12, and cyclic olefins with a carbon number of 5-12.

[0021] In some embodiments, the non-polar solvent and / or weak polar solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane and 1-hexene.

[0022] In some embodiments, the non-polar / weakly polar solvent comprises one of a linear, branched, and cyclic saturated hydrocarbon and an olefin having a carbon number of 5 to 12. In some preferred embodiments, the solvent is one of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane, and 1-hexene.

[0023] In some embodiments, the first solvent includes one or more of straight-chain alkanes with a carbon number of 5-12, branched-chain alkanes with a carbon number of 5-12, cyclic saturated alkanes with a carbon number of 5-12, straight-chain olefins with a carbon number of 5-12, branched-chain olefins with a carbon number of 5-12, and cyclic olefins with a carbon number of 5-12.

[0024] In some embodiments, the first solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane and 1-hexene.

[0025] In some embodiments, the first solvent comprises one of a linear, branched, and cyclic saturated hydrocarbon and an olefin having a carbon number of 5 to 12. In some preferred embodiments, the first solvent is one of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane, and 1-hexene.

[0026] In some embodiments, the concentration of the vegetable oil deodorization distillate in the raw material liquid is 0.1g / L-500g / L, for example, 1g / L, 5g / L, 10g / L, 20g / L, 30g / L, 40g / L, 50g / L, 60g / L, 70g / L, 80g / L, 90g / L, 100g / L, 110g / L, 120g / L, 130g / L, 140g / L, 150g / L, 160g / L, 170g / L, 180g / L, 190g / L, 200g / L, 210g / L, 220g / L, 230g / L, 240g / L, 250g / L, 260g / L, 270g / L, 280g / L, 290g / L, 300g / L, 310g / L, 320g / L, 330g / L, 340g / L, 350g / L, 360g / L, 370g / L, 380g / L, 390g / L, 400g / L, 410g / L, 420g / L, 430g / L, 440g / L, 450g / L, 460g / L, 470g / L, 480g / L, 490g / L, or any value therebetween.

[0027] In some embodiments, the concentration of the raw material solution formed by dissolving the raw material in the first solvent, such as a non-polar solvent, is 0.1-500 g / L, such as 0.5 g / L, 6 g / L, 20 g / L, 100 g / L, 500 g / L or any value therebetween. In some preferred embodiments, the concentration of the vegetable oil deodorization distillate in the raw material solution is 5-400 g / L.

[0028] In some embodiments, the method further comprises mixing the deodorized distillate of plant oil containing squalene with the first solvent, cooling and filtering to obtain a filter cake and a filtrate, drying the filter cake to obtain a plant sterol mixture, and using the filtrate as a raw material liquid for subsequent fractionation extraction.

[0029] In some embodiments, the temperature after the cooling treatment is -20°C to 10°C, for example, -15°C, -10°C, -5°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C or any value therebetween. In some embodiments, the temperature after the cooling treatment is 0°C-7°C.

[0030] In some embodiments, due to the low solubility of the phytosterols in the raw material in the non-polar / weakly polar solvent, the raw material cannot be completely dissolved in the non-polar / weakly polar solvent after being fully stirred with the raw material solvent. In this case, the raw material liquid that is not fully dissolved is cooled to -20°C-10°C, filtered after standing for 5-24 hours, and the filtrate is collected for subsequent fractional extraction, and the filter cake is collected and dried to obtain a phytosterol mixture.

[0031] In some embodiments, the second solvent includes one or more of water, polar solvents of alcohols, polar solvents of sulfones, polar solvents of ketones, polar solvents of amides, polar solvents of nitrile, and furfural. In some embodiments, the second solvent is selected from one or more of water, methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and furfural.

[0032] In some embodiments, the second solvent includes a monopolar solvent and / or a dipolar solvent.

[0033] In some embodiments, the monovalent polar solvent is selected from one of water, alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural. In some embodiments, the monovalent polar solvent is selected from one of methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or furfural.

[0034] In some embodiments, the binary polar solvent is selected from any two of alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural. In some embodiments, the binary polar solvent is selected from two of methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or furfural.

[0035] In some embodiments, the binary polar solvent is selected from a mixed solvent comprising water, wherein the mixed solvent includes water and any polar solvent selected from alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural.

[0036] In some embodiments, the molar fraction of water in the mixed solvent is less than or equal to 50%. In some embodiments, the binary polar solvent is selected from water and any polar solvent selected from methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and furfural.

[0037] In some embodiments, the polar solvent is selected from a monopolar solvent or a binary polar solvent. In some embodiments, the monopolar solvent in the polar solvent includes organic solvents such as water, alcohols, sulfones, ketones, amides, nitriles, furfural, etc., and the binary solvent is a mixed solvent composed of two or one of the above polar organic solvents and water in any proportion. In some preferred embodiments, the monopolar solvent is one of methanol, dimethyl sulfoxide, cyclopentane sulfone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and furfural. The binary solvent is preferably a mixed solvent composed of two of the above solvents in any proportion or one of the above solvents and water, wherein the molar fraction of water is ≤50%.

[0038] In some embodiments, the third solvent includes one or more of straight-chain alkanes with a carbon number of 5-12, branched-chain alkanes with a carbon number of 5-12, cyclic saturated alkanes with a carbon number of 5-12, straight-chain olefins with a carbon number of 5-12, branched-chain olefins with a carbon number of 5-12, and cyclic olefins with a carbon number of 5-12.

[0039] In some embodiments, the third solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane and 1-hexene.

[0040] In some embodiments, the detergent includes one or more of straight-chain alkanes with a carbon number of 5-12, branched-chain alkanes with a carbon number of 5-12, cyclic saturated alkanes with a carbon number of 5-12, straight-chain olefins with a carbon number of 5-12, branched-chain olefins with a carbon number of 5-12, and cyclic olefins with a carbon number of 5-12.

[0041] In some embodiments, the detergent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane and 1-hexene.

[0042] In some embodiments, the detergent is the same as the first solvent.

[0043] In some embodiments, in the fractional extraction, the flow ratio of the raw material liquid to the extractant is 1:(0.1-30), for example 1:0.5, 1:1, 1:3, 1:5, 1:7, 1:10, 1:11, 1:13, 1:15, 1:17, 1:20, 1:21, 1:23, 1:25, 1:27 or any value therebetween.

[0044] In some embodiments, in the fractional extraction, the flow ratio of the raw material liquid to the detergent is 1: (0.01-10), such as 1: 0.03, 1: 0.05, 1: 0.07, 1: 0.1, 1: 0.3, 1: 0.5, 1: 0.7, 1: 1, 1: 1.5, 1: 2, 1: 2.5, 1: 3, 1: 3.5, 1: 4, 1: 4.5, 1: 5, 1: 5.5, 1: 6, 1: 6.5, 1: 7, 1: 7.5, 1: 8, 1: 8.5, 1: 9, 1: 9.5 or any value therebetween. In some embodiments, in the fractional extraction, the flow ratio of the raw material liquid to the detergent is 1: (0.01-5). In some embodiments, in the fractional extraction, the flow ratio of the raw material liquid to the detergent is 1: (0.01-1).

[0045] In some embodiments, when fractional extraction is performed, taking into account factors such as product purity, recovery rate, production cost, etc., the flow ratio of the raw material liquid, the extractant and the detergent is 1: (0.1-30): (0.01-10). In some preferred embodiments, the flow ratio of the raw material liquid, the extractant and the detergent is 1: (1-20): (0.05-5). In some preferred embodiments, the flow ratio of the raw material liquid, the extractant and the detergent is 1: (1-20): (0.05-1).

[0046] The flow ratio in this application refers to the volume ratio of each component.

[0047] In some embodiments, the operating temperature of the fractional extraction is 20°C-70°C, for example, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C or any value therebetween. If the temperature is too low, the viscosity of the raw material solution is large at the concentration, and the mass transfer rate is reduced; if the temperature is too high, the solvent evaporates seriously, affecting the separation effect. It is worth noting that the operating temperature cannot be higher than the boiling point of the selected non-polar / weakly polar solvent and polar solvent.

[0048] In some embodiments, the method further comprises concentrating the raffinate of the fractional extraction, obtaining a recyclable raw material first solvent and / or detergent in the liquid phase, and obtaining squalene after drying the solid phase.

[0049] In some embodiments, the method further comprises separating the extract of the fractionation extraction to obtain a recyclable extractant and a deodorized distillate of vegetable oil from which squalene has been removed, wherein the separation treatment is selected from vacuum concentration, flash evaporation or stripping. In some embodiments, the extractant in the stripping is selected from the same solvent as the first solvent and / or the detergent.

[0050] In some embodiments, the method further comprises vacuum concentrating and drying the raffinate of the fractionation extraction to obtain squalene; vacuum concentrating / flash evaporating / strip extracting the extract of the fractionation extraction with the same solvent as the raw material solvent and detergent, recovering the extractant and recycling it.

[0051] In some embodiments, the fractionation extraction is a multi-stage fractionation extraction. In some embodiments, the fractionation extraction is performed in a fractionation extraction setup. In some embodiments, the fractionation extraction equipment comprises an extraction section and a washing section.

[0052] In some embodiments, the theoretical number of stages of the extraction section is 4-20, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19. In some embodiments, the theoretical number of stages of the washing section is 2-15, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0053] In some embodiments, the extractant enters the fractionation extraction system from the first stage of the extraction section, the raw liquid enters the fractionation extraction system from the last stage of the extraction section, the detergent enters the fractionation extraction system from the first stage of the washing section, the raw liquids are combined at the last stage of the extraction section and enter the extraction section together, the extraction phase and the washing phase are subjected to multi-stage countercurrent contact, and a raffinate enriched in squalene flows out from the first stage of the extraction section, and the raffinate is collected. The raffinate is preferably subjected to vacuum concentration-drying to obtain squalene and a recyclable non- / weakly polar solvent (first solvent and / or detergent); an extract enriched in other components of the vegetable oil deodorization distillate flows out from the first stage of the washing section, and the extract is preferably subjected to vacuum concentration / flash evaporation / strip extraction to recover the extractant and recycle it.

[0054] In some embodiments, the absolute purity and yield of squalene obtained by the present application are both >92 wt.%, and in some preferred embodiments, products with an absolute purity and yield of squalene of >95 wt.% can be obtained.

[0055] In some embodiments, the method comprises the following steps:

[0056] (1) preparing a raw material liquid with a deodorized plant oil distillate containing squalene and a raw material solvent (first solvent); if the raw material cannot be completely dissolved, cooling the mixture and filtering it, collecting the filtrate for subsequent fractional extraction; using a monovalent or divalent polar solvent as an extractant and using the same solvent as the raw material solvent as a detergent for fractional extraction; the fractional extraction is divided into an extraction section and a washing section, the extractant enters the fractional extraction system from the first stage of the extraction section, the raw material liquid enters the fractional extraction system from the last stage of the extraction section, the detergent enters the fractional extraction system from the first stage of the washing section, the raw material liquids are combined at the last stage of the extraction section and enter the extraction section together, the extraction phase and the washing phase are in multi-stage countercurrent contact, a raffinate enriched in squalene flows out from the first stage of the extraction section, and an extract enriched in other components of the deodorized plant oil distillate flows out from the first stage of the washing section;

[0057] (2) vacuum concentrating and drying the raffinate in step (1) to obtain squalene and a recyclable raw material solvent; vacuum concentrating / flash evaporating / stripping with a solvent that is the same as the raw material solvent and the detergent to obtain a recyclable extractant and a deodorized distillate of vegetable oil from which squalene has been removed.

[0058] The advantages of this application are:

[0059] 1. This application is based on the polarity difference caused by the structural difference of phytosterols, tocopherols and fatty esters in squalene and vegetable oil deodorization distillates, and uses a non- / weakly polar solvent-polar solvent as a liquid-liquid two-phase system for fractional extraction, which has a good separation and selection ability for weakly polar squalene;

[0060] 2. The process route proposed in this application has a simple process flow, low energy consumption, high recovery rate and purity of squalene, large processing capacity, and is easy to scale up;

[0061] 3. The present application preferably uses the waste of vegetable oil deodorization distillate from which tocopherol and / or phytosterol has been removed as raw material, and while obtaining high-purity squalene, the phytosterol in the vegetable oil distillate can be recovered, thereby achieving comprehensive utilization of the vegetable oil deodorization distillate. DETAILED DESCRIPTION

[0062] The present application provides a method for separating squalene from vegetable oil deodorization distillate with large processing capacity, simple process flow, high product purity and recovery rate. The method is based on the polarity difference between squalene and other components, and constructs a liquid-liquid two-phase system constructed by a non- / weakly polar solvent and a polar solvent for fractional extraction. The weakly polar squalene is enriched in the non- / weakly polar solvent phase, and the polarity of other components is more easily enriched in the polar solvent phase, thereby realizing the molecular identification and separation of squalene in the vegetable oil deodorization distillate.

[0063] The present application is further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application, but not to limit the protection scope of the present application.

[0064] In the following examples, high performance liquid chromatography (HPLC) was used to analyze the concentration of each component of the vegetable oil deodorization distillate. The specific analysis conditions of HPLC were: Waters Sunfire C18 column (4.6 mm × 250 mm, particle size 5 μm), column temperature 30 ° C, mobile phase methanol: isopropanol: formic acid = 9: 1: 0.001 (volume ratio), flow rate 1 mL / min; the detector was an ultraviolet detector and / or a universal charged aerosol detector (Thermo Fisher Scientific), wherein the wavelength of the ultraviolet detector was set to 205 nm and 292 nm, which were the maximum ultraviolet absorption wavelengths of squalene and tocopherol, respectively.

[0065] In the following examples, the purity and recovery of squalene are calculated as follows:

[0066] Purity = mass of squalene in the product / total mass of the product × 100%

[0067] Yield = total mass of squalene in the product / total mass of squalene in the raw material × 100%

[0068] Example 1

[0069] The deodorized distillate of soybean oil from which tocopherol has been removed (the squalene content of which is 26.0 wt%) is used as a raw material, and it is mixed with n-hexane to form a 50 g / L raw material solution. The raw material is not completely dissolved. The raw material solution is cooled to 4°C, allowed to stand for 12 hours, filtered, and the filter cake is washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0070] The filtrate was collected, and fractional extraction was performed at 30°C using dimethyl sulfoxide as an extractant and n-hexane as a detergent, with the flow ratio of the raw material liquid, the extractant, and the detergent being 1:8.1:0.3 (v / v / v). The theoretical numbers of the extraction section and the washing section were 8 and 4, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material liquid entered the last stage of the extraction section, and the detergent entered the first stage of the washing section. A raffinate rich in squalene flowed out from the first stage of the extraction section, and an extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected separately.

[0071] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 96.3wt%, and the recovery rate is 94.4%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0072] Example 2

[0073] The deodorized olive oil distillate (with squalene content of 29.8 wt%) from which tocopherol and phytosterol are removed is used as a raw material, and it is mixed with cyclopentane to form a 300 g / L raw material liquid, and the raw material is completely dissolved. A binary solvent constructed by methanol and dimethylformamide (the molar fraction of dimethylformamide is 10%) is used as an extractant, and n-hexane is used as a detergent. The flow ratio of the raw material liquid, the extractant, and the detergent is 1:5.4:0.15 (v / v / v), and fractional extraction is performed at 40°C, and the theoretical stages of the extraction section and the washing section are 12 and 4, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid from the last stage of the extraction section, and the detergent from the first stage of the washing section. A raffinate rich in squalene flows out from the first stage of the extraction section, and an extract rich in other components flows out from the first stage of the washing section, and the extract and the raffinate are collected respectively.

[0074] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 93.1wt%, and the recovery rate is 92.5%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0075] Example 3

[0076] The deodorized distillate of soybean oil with tocopherol removed (wherein the squalene content is 26.0wt%) is used as a raw material, and it is mixed with 1-octene to form a 5g / L raw material liquid, and the raw material is completely dissolved. Acetonitrile is used as an extractant, 1-octene is used as a detergent, and the flow ratio of the raw material liquid, the extractant, and the detergent is 1:18.2:0.08 (v / v / v). Fractional extraction is carried out at 20°C, and the theoretical numbers of the extraction section and the washing section are 15 and 2, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid enters the last stage of the extraction section, and the detergent enters the first stage of the washing section. The raffinate rich in squalene flows out from the first stage of the extraction section, and the extract rich in other components flows out from the first stage of the washing section, and the extract and the raffinate are collected respectively.

[0077] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 95.3wt%, and the recovery rate is 94.0%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0078] Example 4

[0079] The deodorized distillate of amaranth seed oil enriched with squalene (wherein the squalene content is 40.3wt%) is used as a raw material, and it is mixed with isooctane to form a raw material liquid of 80g / L, and the raw material is completely dissolved. N-methylpyrrolidone is used as an extractant, and isooctane is used as a detergent. The flow ratio of the raw material liquid, the extractant, and the detergent is 1:5.0:0.2 (v / v / v). Fractional extraction is carried out at 35°C, and the theoretical numbers of the extraction section and the washing section are 15 and 4, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid enters the last stage of the extraction section, and the detergent enters the first stage of the washing section. The raffinate rich in squalene flows out from the first stage of the extraction section, and the extract rich in other components flows out from the first stage of the washing section. The extract and the raffinate are collected separately.

[0080] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 94.6wt%, and the recovery rate is 95.2%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0081] Example 5

[0082] The deodorized distillate of amaranth seed oil enriched with squalene (wherein the squalene content is 40.3wt%) is used as a raw material, and it is mixed with methylcyclohexane to form a 200g / L raw material liquid, and the raw material is completely dissolved. Furfural is used as an extractant, and methylcyclohexane is used as a detergent, and the flow ratio of the raw material liquid, the extractant, and the detergent is 1:11:1 (v / v / v). Fractional extraction is carried out at 25°C, and the theoretical numbers of the extraction section and the washing section are 16 and 12, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid enters the last stage of the extraction section, and the detergent enters the first stage of the washing section. The raffinate rich in squalene flows out from the first stage of the extraction section, and the extract rich in other components flows out from the first stage of the washing section, and the extract and the raffinate are collected respectively.

[0083] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 94.4wt%, and the recovery rate is 95.2%; the extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0084] Example 6

[0085] The deodorized distillate of rice bran oil from which tocopherol has been removed (the squalene content of which is 24.0 wt%) is used as a raw material, and it is mixed with n-octane to form a 400 g / L raw material solution. The raw material is not completely dissolved. The raw material solution is cooled to 4° C., allowed to stand for 12 hours, filtered, and the filter cake is washed twice with a small amount of icy n-octane and then vacuum dried to obtain phytosterols.

[0086] The filtrate is collected, and an acetonitrile aqueous solution with a molar fraction of water of 5% is used as an extractant, and n-octane is used as a detergent, and the flow ratio of the raw material liquid, the extractant, and the detergent is 1:20:0.7 (v / v / v). Fractional extraction is performed at 55°C, and the theoretical numbers of the extraction section and the washing section are 19 and 6, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid enters the last stage of the extraction section, and the detergent enters the first stage of the washing section. The raffinate rich in squalene flows out from the first stage of the extraction section, and the extract rich in other components flows out from the first stage of the washing section. The extract and the raffinate are collected separately.

[0087] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 93.1wt%, and the recovery rate is 93.4%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0088] Example 7

[0089] Using the deodorized distillate of soybean oil from which tocopherol has been removed (wherein the squalene content is 24.0 wt%) as a raw material, it was mixed with n-hexane to form a 400 g / L raw material solution. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, allowed to stand for 12 hours, and filtered. The filter cake was washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0090] The filtrate is collected, and fractional extraction is performed at 30°C using an acetonitrile aqueous solution with a molar fraction of water of 5% as an extractant and n-hexane as a detergent, with the flow ratio of the raw material liquid, the extractant, and the detergent being 1:20:1 (v / v / v). The theoretical numbers of the extraction stage and the washing stage are 19 and 6, respectively. The extractant enters the fractional extraction device from the first stage of the extraction stage, the raw material liquid enters the last stage of the extraction stage, and the detergent enters the first stage of the washing stage. A raffinate rich in squalene flows out from the first stage of the extraction stage, and an extract rich in other components flows out from the first stage of the washing stage. The extract and the raffinate are collected separately.

[0091] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 92.7wt%, and the recovery rate is 94.5%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0092] Example 8

[0093] Using the deodorized distillate of soybean oil from which tocopherol has been removed (wherein the squalene content is 24.0 wt%) as a raw material, it was mixed with n-hexane to form a 400 g / L raw material solution. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, allowed to stand for 12 hours, and filtered. The filter cake was washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0094] The filtrate is collected, and fractional extraction is performed at 30° C. using an acetonitrile aqueous solution with a molar fraction of water of 5% as an extractant and n-hexane as a detergent, with the flow ratio of the raw material liquid, the extractant, and the detergent being 1:10:0.7 (v / v / v). The theoretical numbers of the extraction stage and the washing stage are 19 and 6, respectively. The extractant enters the fractional extraction device from the first stage of the extraction stage, the raw material liquid enters the last stage of the extraction stage, and the detergent enters the first stage of the washing stage. A raffinate rich in squalene flows out from the first stage of the extraction stage, and an extract rich in other components flows out from the first stage of the washing stage. The extract and the raffinate are collected separately.

[0095] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 90.1wt%, and the recovery rate is 98.6%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0096] Example 9

[0097] Using the deodorized distillate of soybean oil from which tocopherol has been removed (wherein the squalene content is 24.0 wt%) as a raw material, it was mixed with n-hexane to form a 400 g / L raw material solution. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, allowed to stand for 12 hours, and filtered. The filter cake was washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0098] The filtrate is collected, and fractional extraction is performed at 30°C using an acetonitrile aqueous solution with a molar fraction of water of 5% as an extractant and n-hexane as a detergent, with the flow ratio of the raw material liquid, the extractant, and the detergent being 1:15:0.7 (v / v / v). The theoretical numbers of the stages of the extraction section and the washing section are 19 and 6, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid enters the last stage of the extraction section, and the detergent enters the first stage of the washing section. A raffinate rich in squalene flows out from the first stage of the extraction section, and an extract rich in other components flows out from the first stage of the washing section. The extract and the raffinate are collected separately.

[0099] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 92.0wt%, and the recovery rate is 94.5%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0100] Example 10

[0101] Using the deodorized distillate of soybean oil from which tocopherol has been removed (wherein the squalene content is 24.0 wt%) as a raw material, it was mixed with n-hexane to form a 400 g / L raw material solution. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, allowed to stand for 12 hours, and filtered. The filter cake was washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0102] The filtrate is collected, and fractional extraction is performed at 30° C. using an acetonitrile aqueous solution with a molar fraction of water of 5% as an extractant and n-hexane as a detergent, with the flow ratio of the raw material liquid, the extractant, and the detergent being 1:20:0.7 (v / v / v). The theoretical numbers of the extraction stage and the washing stage are 12 and 8, respectively. The extractant enters the fractional extraction device from the first stage of the extraction stage, the raw material liquid enters the last stage of the extraction stage, and the detergent enters the first stage of the washing stage. A raffinate rich in squalene flows out from the first stage of the extraction stage, and an extract rich in other components flows out from the first stage of the washing stage. The extract and the raffinate are collected separately.

[0103] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 93.0wt%, and the recovery rate is 90.6%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0104] Embodiment 11

[0105] Using the deodorized distillate of soybean oil from which tocopherol has been removed (the squalene content of which is 40.3wt%) as a raw material, it was mixed with n-hexane to form a 400g / L raw material solution. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, allowed to stand for 12 hours, and filtered. The filter cake was washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0106] The filtrate is collected, and fractional extraction is performed at 30°C using an acetonitrile aqueous solution with a molar fraction of water of 5% as an extractant and n-octane as a detergent, with the flow ratio of the raw material liquid, the extractant, and the detergent being 1:20:0.7 (v / v / v). The theoretical numbers of the stages of the extraction section and the washing section are 19 and 6, respectively. The extractant enters the fractional extraction device from the first stage of the extraction section, the raw material liquid enters the last stage of the extraction section, and the detergent enters the first stage of the washing section. A raffinate rich in squalene flows out from the first stage of the extraction section, and an extract rich in other components flows out from the first stage of the washing section. The extract and the raffinate are collected separately.

[0107] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 99.9wt%, and the recovery rate is 93.4%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0108] Comparative Example 1

[0109] The deodorized distillate of soybean oil from which tocopherol has been removed (the squalene content of which is 26.0 wt%) is used as a raw material, and it is mixed with n-hexane to form a 50 g / L raw material solution. The raw material is not completely dissolved. The raw material solution is cooled to 4°C, allowed to stand for 12 hours, filtered, and the filter cake is washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterols.

[0110] The filtrate was collected, and dimethyl sulfoxide was used as the extractant, and the flow ratio of the raw liquid to the extractant was 1:8.1 (v / v), and fractional extraction was performed at 30°C. The theoretical number of stages of the extraction section is 8. The extractant enters the extraction device from the first stage of the extraction section, and the raw liquid enters the extraction device from the last stage of the extraction section. The raffinate rich in squalene flows out from the first stage of the extraction section, and the extract rich in other components flows out from the last stage of the extraction section. The extract and the raffinate are collected separately.

[0111] The raffinate is vacuum concentrated, the solvent (raw solvent) is collected for recycling, the solid phase is collected and dried to obtain the squalene product, the purity of squalene is 90.1wt%, and the recovery rate is 70.1%. The extract is vacuum concentrated, the organic solvent (extractant) is collected for recycling.

[0112] The above embodiments are only used to illustrate the technical solution of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments can still be modified, or some or all of the technical features therein can be replaced by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solution to deviate from the scope of the technical solution of the present application.

Claims

1. A method for separating squalene from a deodorized vegetable oil distillate, comprising mixing the deodorized vegetable oil distillate containing squalene with a first solvent to obtain a raw material liquid, and fractionating and extracting the raw material liquid using a second solvent as an extractant and a third solvent as a detergent, in, The first solvent is selected from one or more of non-polar solvents and weak polar solvents, the second solvent is selected from one or more of polar solvents, and the third solvent is selected from one or more of non-polar solvents and weak polar solvents.

2. The method according to claim 1, characterized in that The vegetable oil deodorized distillate containing squalene includes one or more of the whole components of the vegetable oil deodorized distillate or its esterified product, the components of the vegetable oil deodorized distillate or its esterified product except tocopherol and / or phytosterol, and the components of the vegetable oil deodorized distillate enriched with squalene; Preferably, the vegetable oil deodorized distillate containing squalene is selected from the vegetable oil deodorized distillate or the component of its esterification product from which tocopherol and / or phytosterol are removed, or the vegetable oil deodorized distillate enriched with squalene; Preferably, the vegetable oil deodorized distillate is selected from one or more of soybean oil deodorized distillate, rice bran oil deodorized distillate, rapeseed oil deodorized distillate, camellia oil deodorized distillate and olive oil deodorized distillate.

3. The method according to claim 1 or 2, characterized in that: The non-polar solvent and / or weak polar solvent includes one or more of straight-chain alkanes with a carbon number of 5-12, branched-chain alkanes with a carbon number of 5-12, cyclic saturated alkanes with a carbon number of 5-12, straight-chain olefins with a carbon number of 5-12, branched-chain olefins with a carbon number of 5-12 and cyclic olefins with a carbon number of 5-12; preferably one or more selected from cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane and 1-hexene.

4. The method according to any one of claims 1 to 3, characterized in that The concentration of the vegetable oil deodorization distillate in the raw material liquid is 0.1 g / L-500 g / L, preferably 5 g / L-400 g / L.

5. The method according to any one of claims 1 to 4, characterized in that The method further comprises mixing the deodorized distillate of plant oil containing squalene with the first solvent, cooling the mixture, filtering the mixture to obtain a filter cake and a filtrate, drying the filter cake to obtain a plant sterol mixture, and using the filtrate as a raw material for subsequent fractionation extraction; preferably, the temperature after the cooling treatment is between -20°C and 10°C, preferably between 0°C and 7°C.

6. The method according to any one of claims 1 to 5, characterized in that The second solvent includes one or more of water, alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural, preferably one or more of water, methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and furfural; Preferably, the second solvent comprises a monopolar solvent and / or a dipolar solvent, The monovalent polar solvent is selected from one of water, alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural. Preferably, the monovalent polar solvent is selected from one of methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or furfural. The binary polar solvent is selected from any two of alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural; preferably, the binary polar solvent is selected from two of methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or furfural; Alternatively, the binary polar solvent is selected from a mixed solvent containing water, the mixed solvent comprising water and any polar solvent selected from alcohol polar solvents, sulfone polar solvents, ketone polar solvents, amide polar solvents, nitrile polar solvents and furfural. Preferably, in the mixed solvent, the molar fraction of water is less than or equal to 50%; preferably, the binary polar solvent is selected from water and any polar solvent selected from methanol, dimethyl sulfoxide, cyclopentane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and furfural.

7. The method according to any one of claims 1 to 6, characterized in that The third solvent (detergent) is the same as the first solvent.

8. The method according to any one of claims 1 to 7, characterized in that In the fractional extraction, the flow ratio of the raw material liquid, the extractant and the detergent is 1:(0.1-30):(0.01-10), preferably 1:(1-20):(0.05-5).

9. The method according to any one of claims 1 to 8, characterized in that The operating temperature of the fractional extraction is 20°C-70°C.

10. The method according to any one of claims 1 to 9, characterized in that The method further comprises: The raffinate of the fractional extraction is concentrated to obtain a recyclable first solvent and / or detergent in the liquid phase, and squalene is obtained after the solid phase is dried; and / or The extract of the fractional extraction is separated to obtain a recyclable extractant and a deodorized distillate of vegetable oil from which squalene has been removed. The separation treatment is selected from vacuum concentration, flash evaporation or stripping. Preferably, the extractant in the stripping is selected from the same solvent as the first solvent and / or the detergent.